Guerbet raspberry esters as a delivery system for natural antioxidants

ABSTRACT

The present invention relates to raspberry seed oil derivatives derived by the reaction of a guerbet alcohol and cold pressed raspberry seed oil. The choice of cold pressed raspberry seed oil as a raw material in the preparation of the compounds of the present invention is critical, since it has been found that the cold pressed raspberry seed oil contains antioxidants, antimicrobial compounds and which when reacted with a guerbet alcohol result in products that deliver said actives to the skin and hair, resulting in protection of the skin and hair from environmental factors such as acid rain, ozone attack and UV degradation.

BACKGROUND OF THE INVENTION

The present invention relates to raspberry seed oil derivatives derivedby the reaction of specific beta branched alcohols, referred to asguerbet alcohols and cold pressed raspberry seed oil. The choice of coldpressed raspberry seed oil as a raw material in the preparation of thecompounds of the present invention is critical, since it has been foundthat the cold pressed raspberry seed oil contains a unique antioxidantwhich when reacted with a guerbet alcohol result in products thatdeliver said actives to the skin and hair, resulting in protection ofthe skin and hair from environmental factors such as acid rain, ozoneattack and UV degradation.

U.S. Pat. No. 6,391,345 issued May 2002 describes the refining of coldpressed raspberry seed oil, and is incorporated herein by reference.American cranberries, Vaccinium macrocarpon, are native plants of open,acid peat bogs in North America. Raspberry plants are evergreenperennial vines that produce runners and upright branches with terminalflower buds.

Raspberries have historically been harvested and either ingested aswhole berries, such as in raspberry sauce, or have been processed fortheir juice. Pulp remaining after raspberry juice extraction processinghas historically been regarded as an undesirable waste product withlittle or no utility.

Raspberries are grown all over the world. They are a popular food,consumed in large quantities.

Raspberries contain ellagic acid (C₁₄H₆O₈). This acid is a non-flavonoidpolyphenol present in the form of hydrolysable tannins, which has beenfound to protect chromosomes from radiation induced lipid peroxidation.

Raspberry oil contains a high level of omega 3 and omega 6 linoleicacid. These are essential fatty acids. Under normal circumstances, oilsuseful in the cosmetic industry are refined with a variety of steps thatare designed to maximize triglyceride content, and minimize color andodor. These steps include steam distillation, a process in which steamis sparged through the oil to remove odor and color bodies and solventextraction with compounds like hexane, which remove additional odor andcolor bodies. We have learned that these processes, while improvingcolor and odor, remove many of the desirable “active” materials. Whatresults is a light color, low odor triglyceride with no appreciableadded skin benefits. We have surprisingly learned that when theraspberry seed oil that is cold processed is reacted with specificguerbet alcohol compounds, the actives (normally removed in non-coldpress process) remain in the product, become water-soluble and haveoutstanding activity on the skin. In essence two things happen when thecold pressed raspberry seed oil is reacted with dimethicone copolyol.First the triglyceride reacts with the hydroxyl group of the guerbetcompound, giving a oil-soluble ester. Secondly, these specific estersolubilizes the active components there as a consequence of coldpressing. Thirdly, these very desirable materials are deposited on theskin by the ester, based upon its proclivity to remain on the skin. Theresult is a unique delivery of the actives to the skin from totallynatural fruit oil.

Guerbet alcohols have been known for many years, primarily for theirliquidity at high molecular weight. Over the years there have been anumber of derivatives patented. U.S. Pat. No. 4,868,236 to O'Lenickdiscloses a guerbet citric ester and polymers thereof useful in plasticlubrication. U.S. Pat. No. 5,488,121 issued Jan. 30, 1996 to O'Lenickteaches that esters based upon a guerbet acid and guerbet alcohol havesurprisingly good liquidity. However these patents did not disclose orsuggest the possibility of using cold pressed raspberry seed oil that isrich in antioxidants and other actives that could be delivered to theskin using a specific ester as a delivery molecule.

SUMMARY OF THE INVENTION

The present invention relates to a series of guerbet esters derived fromthe reaction of cold pressed raspberry oil and specific guerbetalcohols.

The present invention also relates to a process of treating hair andskin, which comprises contacting the hair and skin with an effectiveanti-oxidant containing amount of a raspberry guerbet ester of thepreset invention.

DETAILED DESCRIPTION OF THE INVENTION

U.S. Pat. No. 6,391,345 issued May 2002 describes a cold pressed processfor cranberry oil. We have surprisingly found that if the same processis used on raspberry oil specific antioxidant materials that are removedby more aggressive refining processes like solvent extraction. Thesecompounds surprisingly survive the reaction with guerbet alcohol resultin an oil soluble, highly substantive delivery system for these verydesirable natural compounds.

Also critical to the practice of the present invention is the fattycomposition of the cold pressed raspberry oil. This raspberry oil has asubstantially clear appearance with a pale yellow color.

Cold Pressed Raspberry Oil is a triglyceride conforming to the followingstructure:

The oil is referred to as Rubus idaeus seed oil and has a CAS number of381718-28-1

The R—C(O)— group has the following composition:

Component % Weight 18:1 oleic 10–20 18:2 linoleic 30–40 18:3 linolenic(alpha) 45–55 alpha tocopherol 46 mg/gram Ellagic Acid 450–650 ppm

Distribution by type of fatty group

Component % Weight Saturated  3% Polyunsaturated content 86% Monounsaturated 11%

The oil contains the following very critical “active” components forskin and hair care:

Material Concentration 18:3 linolenic (alpha) 45–55% alpha tocopherol 46mg/gram Ellagic Acid 450–650 ppm

As can be seen, the cold pressed raspberry seed oil is a rich source ofcompounds having important properties when applied to hair and skin. Thecold pressed raspberry oil can shield against UV-A induced damage byscattering light as well as by light spectrum absorption. The coldpressed raspberry oil has, then activity as a broad spectrum UVprotectant. The raspberry oil may be used alone or in combination withother conventional sunscreens, (emphasis Added)

The ability to make derivatives of the oil in which the protection ofthe components of the cold pressed oil remain functional is a majoraspect of the present invention.

Cold pressed raspberry seed oil has a very high concentration of gammatocopherol. This level is much higher than is found in oils such assafflower and grape, which are 11 and 33, respectively. The gammatocopherol has the most antioxidant capacity of all of the tocopherolsand contributes to the stability of highly unsaturated oils in theraspberry oil. It is believed that the presence of the high gammatocopherol concentration makes raspberry oil an excellent additive toanimal food-both human and non-human. The gamma tocopherol may be asimportant as alpha tocopherol in preventing degenerative diseases.

Cold pressed raspberry seed oil has a high linolenic acid content.Linolenic acid has been implicated as a food additive and nutraceuticalin preventing coronary heart disease and cancer. Raspberry oil also hasa high polyunsaturated: saturated ratio in a neutral lipid fraction, of10:1. This ratio is regarded as having value in reducing serumcholesterol, atherosclerosis and in preventing heart disease.

Cold pressed raspberry seed oil has a rather dark yellow to orange colorbecause it contains carotenoids. The carotenoids are usable as colorantsubstitutes for materials such as carotenes, annotos, and apocarotenalsused in the nutraceutical and oil industries.

The cold pressed raspberry seed oil, containing all of the abovedesirable compounds, is reacted with a guerbet alcohol conforming to thefollowing structure:

whereina is an integer ranging from 5 to 17;b is an integer ranging from 3 to 15.

To provide an ester conforming to the following structure:R—C(O)OR′R derived from cold pressed raspberry seed oil and has the composition;

Component % weight 18:1 oleic 10–20 18:2 linoleic 30–40 18:3 linolenic(alpha) 45–55 alpha tocopherol 46 mg/gram Ellagic Acid 450–650 ppm

R′ is

a is an integer ranging from 5 to 17;b is an integer ranging from 3 to 15.

The current invention describes a composition, which is prepared by thereaction esterification reaction of:

(1) cold pressed raspberry seed oil

(2) a guerbet alcohol conforming to the following structure

wherein;a is an integer ranging from 5 to 17;b is an integer ranging from 3 to 15.

The compounds of the present invention deliver these active products toskin, therefore the invention also discloses a process for conditioningskin which comprises contacting the skin with an effective conditioningconcentration of a raspberry guerbet ester, which conforms to thefollowing structure;R—C(O)OR′wherein;R is derived from cold pressed raspberry seed oil;R′ is;

a is an integer ranging from 5 to 17;b is an integer ranging from 3 to 15. The effective conditioningconcentration ranges from 0.01 to 15.0% by weight.

Preferred Embodiment

In a preferred embodiment a is 5 and b is 3.

In a preferred embodiment a is 7 and b is 5.

In a preferred embodiment a is 9 and b is 7.

In a preferred embodiment a is 11 and b is 9.

In a preferred embodiment a is 13 and b is 11.

In a preferred embodiment a is 17 and b is 15.

EXAMPLES

The compounds of the present invention are made from commerciallyavailable raw materials.

Raw Materials

Cold Pressed Raspberry Seed Oil

Cold Presses Raspberry seed oil is an item of commerce sold by RegalTrade & Consult LLC. of Hoboken, N.J. It is processed using U.S. Pat.No. 6,391,345 issued May 2002, only applied to raspberry seed oil notcranberry seed oil.

Guerbet Alcohols

Condea Chemical produces guerbet alcohols commercially. The values of aand b were actually determined by analysis and are not dependant upontrade name for meaning.

Example Commercial Name a b Chemical Name 1 Isofol 12 5 32-butyl-octanol 2 Isofol 16 7 5 2-hexyl-decanol 3 Isofol 20 9 72-octyl-dodecanol 4 Isofol 24 11 9 2-decyl-tetradecanol 5 Isofol 28 1311 2-dodecyl-hexadecanol 6 Isofol 36 17 15 2-hexadecyl-eicosonol

General Procedure

To grams of 400 grams of Cold Pressed Raspberry seed oil is added thespecified amount of the specified guerbet alcohol (examples 1–10). Next0.1% of a suitable esterification catalyst is added. The catalyst isselected from the group consisting of methane sulfonic acid, tincompounds and titinate compounds. The preferred catalyst is dilauryl tinoxide.

The reaction mass is heated to 180–200 C, under good agitation. As thereaction mass is held at temperature, the material clears and becomeshomogeneous. The reaction mass is held for eight hours at reactiontemperature, then cooled to ambient. Upon standing, the glycerin formedseparates into from the product and is removed by decanting. Theresulting product is in the other phase and is used without additionalpurification.

Guerbet Alcohol Example Example Grams 11 1 186.0 12 2 242.0 13 3 298.014 4 354.0 15 5 410.0 16 6 522.0

The products of examples 1–3 are liquid at ambient temperatures. Theproducts 4–6 are pastes.

Applications Examples

The compounds of the present invention are oil-soluble compounds thathave an extraordinary skin feel and provide antioxidant, and otherdesirable properties from the components that are not removed from theraspberry oil when it is cold processed. The cold processing leavesbehind the desirable components, which in turn are not destroyed by thereaction and surprisingly, become oil-soluble and delivered to the skin.

In addition to delivering the desirable compounds to the surface of theskin, the compounds are breathable and provide moisturizing andemmoliency to the skin.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthhereinabove but rather that the claims be construed as encompassing allthe features of patentable novelty which reside in the presentinvention, including all features which would be treated as equivalentsthereof by those skilled in the art to which the invention pertains

1. A raspberry guerbet ester, which conforms to the following structure;R—C(O)OR′ wherein; R is derived from cold pressed raspberry seed oil; R′is;

a is an integer ranging from 5 to 17; b is an integer ranging from 3 to15, wherein the R—C(O)— group has the following composition: Component %Weight 18:1 oleic 10–20 18:2 linoleic 30–40 18:3 linolenic (alpha) 45–55alpha tocopherol 46 mg/gram Ellagic Acid 450–650 ppm.


2. A raspberry guerbet ester of claim 1 wherein a is 5 and b is
 3. 3. Araspberry guerbet ester of claim 1 wherein a is 7 and b is
 5. 4. Araspberry guerbet ester of claim 1 wherein a is 9 and b is
 7. 5. Araspberry guerbet ester of claim 1 wherein a is 11 and b is
 9. 6. Araspberry guerbet ester of claim 1 wherein a is 13 and b is
 11. 7. Araspberry guerbet ester of claim 1 wherein a is 17 and b is
 15. 8. Aprocess for conditioning skin which comprises contacting the skin withan effective conditioning concentration of a raspberry guerbet ester,which conforms to the following structure;R—C(O)OR′ wherein; R is derived from cold pressed raspberry seed oil; R′is;

a is an integer ranging from 5 to 17; b is an integer ranging from 3 to15, wherein the R—C(O)— group has the following composition: Component %Weight 18:1 oleic 10–20 18:2 linoleic 30–40 18:3 linolenic (alpha) 45–55alpha tocopherol 46 mg/gram Ellagic Acid 450–650 ppm.


9. A process of claim 8 wherein said effective conditioningconcentration ranges from 0.01 to 15.0% by weight.
 10. A process ofclaim 9 wherein a is 5 and b is
 3. 11. A process of claim 9 wherein a is7 and b is
 5. 12. A process of claim 9 wherein a is 9 and b is
 7. 13. Aprocess of claim 9 wherein a is 11 and b is
 9. 14. A process of claim 9wherein a is 13 and b is
 11. 15. A process of claim 9 wherein a is 17and b is 15.